CN111020257A - Method for improving purity of nickel cupronickel material - Google Patents
Method for improving purity of nickel cupronickel material Download PDFInfo
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- CN111020257A CN111020257A CN201911309943.1A CN201911309943A CN111020257A CN 111020257 A CN111020257 A CN 111020257A CN 201911309943 A CN201911309943 A CN 201911309943A CN 111020257 A CN111020257 A CN 111020257A
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- nickel
- raw material
- cupronickel
- nickel cupronickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 119
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 93
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 230000006698 induction Effects 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 21
- OPXJEFFTWKGCMW-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Ni].[Cu] OPXJEFFTWKGCMW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims description 47
- 239000002893 slag Substances 0.000 claims description 36
- 239000000155 melt Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims description 6
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000289 melt material Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 26
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 238000005554 pickling Methods 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 description 9
- 239000006184 cosolvent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000011403 purification operation Methods 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- QBAACSOJSANLBS-UHFFFAOYSA-N copper nickel Chemical compound [Ni][Cu][Ni][Cu] QBAACSOJSANLBS-UHFFFAOYSA-N 0.000 description 1
- LDSIKPHVUGHOOI-UHFFFAOYSA-N copper;oxonickel Chemical compound [Ni].[Cu]=O LDSIKPHVUGHOOI-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for improving the purity of a nickel cupronickel material, which comprises the following steps: s1: acid washing: carrying out ultrasonic pickling on nickel cupronickel in absolute ethyl alcohol, putting the pickled nickel cupronickel raw material into electrolyte for electrolysis, and removing an oxide layer on the surface of the nickel cupronickel; s2: putting the pretreated nickel cupronickel raw material into a vacuum induction smelting furnace, carrying out vacuum induction smelting to a molten state, and preparing a solid electrode through a die material; s3: and (4) taking the solid electrode obtained in the step (S2) as a remelting electrode for vacuum consumable remelting, taking a water-cooled copper crucible as a consumable electrode to conduct arc striking between the two electrodes, and electrically melting the solid electrode into the water-cooled copper crucible for cooling to obtain the purified nickel cupronickel. In a word, the method has the advantages of perfect process, high purification efficiency, high purity of the prepared nickel-copper-nickel alloy, and the like.
Description
Technical Field
The invention belongs to the technical field of material purification, and particularly relates to a method for improving the purity of a nickel-copper-nickel alloy material.
Background
The cupronickel is a copper-based alloy with nickel as a main additive element, is silvery white and has metallic luster, so the cupronickel is named as cupronickel. The pure copper plus nickel can obviously improve the strength, corrosion resistance, hardness, resistance and thermoelectricity, and reduce the temperature coefficient of resistivity. Therefore, compared with other copper alloys, the cupronickel has the advantages of excellent mechanical property and physical property, good ductility, high hardness, beautiful color, corrosion resistance and deep drawing property, is widely used in the fields of shipbuilding, petrochemical industry, electrical appliances, instruments, medical appliances, daily necessities, artware and the like, and is also an important resistance and thermocouple alloy.
x-rays are widely used in various fields such as medical care, health, industry and agriculture, national defense and the like. In order to better generate, effectively control and safely utilize the X-ray, the X-ray bulb tube with high vacuum is required to be developed according to the principle. X-ray tubes are essential main elements in x-ray machines for medical use.
However, the impurities in the nickel cupronickel affect the metallic properties of the nickel cupronickel due to unavoidable impurities in the production process and materials, so that the nickel cupronickel does not meet the preparation requirements when manufacturing the medical x-ray tube, and may cause damage and danger to the x-ray tube during use. Therefore, the invention provides a method for improving the purity of the nickel cupronickel material.
Disclosure of Invention
Aiming at the problems, the invention provides a method for improving the purity of a nickel cupronickel material.
The technical scheme of the invention is as follows: a method for improving the purity of a nickel cupronickel material mainly comprises the following steps:
s1: pretreatment of
Acid washing: completely immersing the nickel-copper-nickel raw material in absolute ethyl alcohol, carrying out acid washing for 10-20min by using an ultrasonic cleaning device, and cleaning and drying the nickel-copper-nickel raw material;
surface treatment: placing the acid-washed nickel cupronickel raw material in electrolyte, and introducing current with density of 3-5A/cm2The current is used for carrying out surface layer electrolysis on the nickel cupronickel to remove an oxide layer on the surface of the nickel cupronickel, and a high-power blower is used for cleaning the surface of the nickel cupronickel;
s2: vacuum induction melting
Placing the pretreated nickel-copper oxide raw material in a vacuum induction melting furnace, preheating 800-900K, and continuously introducing argon with the purity of 99.99 percent in the preheating processAfter preheating, vacuum induction melting and vacuumizing to 3-5 multiplied by 10-1Pa, heating to 1200-1300K, carrying out vacuum induction melting on the nickel cupronickel raw material to a molten state, and preparing a solid electrode through a mold material;
s3: vacuum consumable remelting
And (4) taking the solid electrode obtained in the step (S2) as a remelting electrode for vacuum consumable remelting, taking a water-cooled copper crucible as a consumable electrode to conduct arc striking between the two electrodes, and electrically melting the solid electrode into the water-cooled copper crucible for cooling to obtain the purified nickel cupronickel.
Preferably, the electrolyte in the S1 consists of 2-3% of hydrochloric acid, 1-2% of oxalic acid, 3-5% of citric acid, 1-2% of ammonium sulfate and the balance of deionized water, and can quickly remove an oxide layer on the surface of the nickel cupronickel.
Further, the raw material of nickel cupronickel in S1 can be subjected to slagging and impurity removal processes before acid cleaning according to the purity of the raw material: the method comprises the steps of heating a nickel cupronickel raw material to 1000-1200K to obtain a melt raw material, adding a mixed slagging agent into the melt raw material, reacting the mixed slagging agent with impurities in the melt raw material to generate oxide residues, removing the oxide residues floating on the surface of the melt raw material by using slagging-off equipment until no obvious oxide residues exist on the surface of the melt, cooling the remaining melt raw material to obtain the nickel cupronickel raw material after impurity removal, wherein a metal oxide layer can be formed on the surface of the nickel cupronickel raw material in the production, transportation and storage processes of the conventional industrial nickel cupronickel raw material, the purity of the conventional industrial nickel cupronickel raw material is low, and the nickel cupronickel raw material is subjected to primary impurity removal before pretreatment, so that subsequent purification is facilitated, and the purification efficiency.
Preferably, the mass ratio of the mixed slag former to the melt raw material is 1:5-8, so that impurities in the nickel cupronickel material are fully removed.
Preferably, the mixed slag former in S2 is a cone-shaped material formed by pressing a slag former, a cosolvent and a protective agent in a mass ratio of 10:9:2, and the slag former is CaO and SiO2The cosolvent is CaCl in a mass ratio of 1-2:12The protective agent consists of borax and magnesium in a ratio of 3-4:1, and the cone-shaped material can naturally settle to a melt raw material under the action of gravityThe mixed slag former can react with metal impurities in the nickel cupronickel raw material to generate oxide impurities, the cosolvent can reduce the viscosity of the mixed slag former, the reaction rate is increased, the removal rate of the metal impurities is improved, the protective agent can form a protective layer on the surface of the melt raw material, and the melt raw material is prevented from undergoing an oxidation reaction with oxygen in the air in subsequent treatment.
Further, the raw material of nickel cupronickel in S1 can be subjected to a powdering and impurity removing process before being subjected to acid washing according to the purity of the raw material: the method comprises the steps of cutting a nickel cupronickel raw material into rod-shaped materials, clamping the rod-shaped materials on a smelting machine, carrying out electrode induction smelting until the rod-shaped materials are melted into liquid, allowing the liquid to fall through a settling tube under the action of gravity, blowing the liquid raw material into fine liquid drops by using high-temperature jet gas, condensing the liquid drops into solid powder in the settling process, sorting the solid powder to obtain nickel cupronickel powder, carrying out cold isostatic pressing on the nickel cupronickel powder to obtain the nickel cupronickel raw material after impurity removal, forming a metal oxide layer on the surface of the nickel cupronickel in the production, transportation and storage processes of the existing industrial nickel cupronickel raw material, and improving the purification efficiency, wherein the purity of the existing industrial nickel cupronickel raw material is low, and the nickel cupronickel raw material is subjected to preliminary impurity removal before pretreatment, so.
Preferably, the high-temperature injection gas is argon with the temperature of 500-600K, the injection speed of the high-temperature injection gas is 300-400m/s, the high-temperature injection gas can break the liquid raw material into fine particles, and the particle size is related to the temperature and the speed of the high-temperature injection gas.
Further, the cold isostatic pressing comprises the following specific processes: and (3) filling the sorted nickel cupronickel powder into a rubber sleeve and sealing, filling the rubber sleeve into a plastic sleeve with the sealing position facing inwards, placing the plastic sleeve into an electrode mould, and performing compression molding under the pressure of 400-plus-500 MPa, wherein the molded solid electrode has high density and uniform distribution.
Preferably, the purified nickel cupronickel prepared in the step S5 is used for manufacturing medical X-ray bulb tubes, and the manufactured X-ray bulb tubes have high strength and long service life.
The invention has the beneficial effects that: the invention provides a method for improving the purity of a nickel cupronickel material, which comprises the steps of pretreating the existing commercial nickel cupronickel to remove an oxide layer on the surface of the nickel cupronickel, avoiding the oxide layer of a selected raw material from influencing the purity of the material, melting the nickel cupronickel by adopting a vacuum induction melting mode, continuously introducing protective gas in a melting preheating process, carrying out melting protection, removing impurity metal steam generated in the melting process by flowing the introduced protective gas, keeping the temperature of a melt raw material, adding a mixed slag former to react with impurities in the melt raw material to generate oxides, removing the oxides, crushing the melt raw material into fine particles by adopting a powder-making impurity-removing process, separating the pure nickel cupronickel material by the mass difference of the nickel cupronickel and the oxide impurities, having high purification efficiency and high purity of the obtained nickel cupronickel material, and finally utilizing vacuum self-consumption remelting to ensure that the nickel cupronickel material is uniformly distributed, The segregation coefficient is low, and the high-temperature resistance and the fatigue resistance of the nickel-copper alloy can be improved. In a word, the method has the advantages of perfect process, high purification efficiency, high purity of the prepared nickel-copper-nickel alloy, and the like.
Detailed Description
In order to facilitate understanding of the technical scheme of the present invention, the present invention is further explained by combining specific examples and experimental examples, which are not to be construed as limiting the scope of the present invention.
Example 1:
a method for improving the purity of a nickel cupronickel material mainly comprises the following steps:
s1: pretreatment of
Acid washing: completely immersing the nickel-copper-nickel raw material in absolute ethyl alcohol, carrying out acid washing for 10-20min by using an ultrasonic cleaning device, and cleaning and drying the nickel-copper-nickel raw material;
surface treatment: placing the acid-washed nickel cupronickel raw material in electrolyte, and introducing current with density of 3-5A/cm2The current is used for carrying out surface layer electrolysis on the nickel cupronickel to remove an oxide layer on the surface of the nickel cupronickel, and a high-power blower is used for cleaning the surface of the nickel cupronickel, wherein the electrolyte consists of 3% of hydrochloric acid, 2% of oxalic acid, 5% of citric acid, 2% of ammonium sulfate and the balance of deionized water;
s2: vacuum induction melting
Placing the pretreated nickel cupronickel raw material into a vacuum induction melting furnace, preheating at 900K, continuously introducing argon with the purity of 99.99 percent in the preheating process, and vacuumizing to 5 multiplied by 10 after the preheating is finished-1Pa, heating to 1300K, carrying out vacuum induction melting on the nickel cupronickel raw material to a molten state, and preparing a solid electrode through a die material;
s3: vacuum consumable remelting
And (4) taking the solid electrode obtained in the step (S2) as a remelting electrode for vacuum consumable remelting, taking a water-cooled copper crucible as a consumable electrode to conduct arc striking between the two electrodes, electrically melting the solid electrode into the water-cooled copper crucible for cooling to obtain purified nickel cupronickel, and applying the purified nickel cupronickel to manufacturing of medical x-ray bulb tubes.
Example 2:
the same as example 1 except that: the method comprises the following steps of carrying out slagging and impurity removal on a nickel cupronickel raw material in S1 before acid washing: heating a nickel cupronickel raw material to 1200K to obtain a melt raw material, adding a mixed slag former into the melt raw material, wherein the mass ratio of the mixed slag former to the melt raw material is 1:8, the mixed slag former is a cone-shaped material formed by pressing the slag former, a cosolvent and a protective agent in a mass ratio of 10:9:2, and the slag former is CaO and SiO2The cosolvent is CaCl in a mass ratio of 1:12The protective agent is composed of borax and magnesium in a ratio of 3:1, the mixed slag former reacts with impurities in the melt raw material to generate oxide residues, the oxide residues floating on the surface of the melt raw material are removed by slag removing equipment until no obvious oxide residues exist on the surface of the melt, and the remaining melt raw material is cooled to obtain the nickel-copper white raw material after impurity removal.
Example 3:
the same as example 1 except that: the nickel cupronickel raw material in S1 is subjected to a powdering and impurity removing process before being subjected to acid washing: cutting a nickel cupronickel raw material into rod-shaped materials, clamping the rod-shaped materials on a smelting machine, smelting by electrode induction until the rod-shaped materials are melted into liquid, allowing the liquid to fall through a settling tube under the action of gravity, blowing the liquid raw material into fine liquid drops by using high-temperature jet gas, wherein the high-temperature jet gas is argon gas of 600K, the jet speed of the high-temperature jet gas is 400m/s, the liquid drops are condensed into solid powder in the settling process, sorting the solid powder to obtain nickel cupronickel powder, carrying out cold isostatic pressing on the nickel cupronickel powder to obtain the nickel cupronickel raw material after impurity removal, and the specific process of the cold isostatic pressing is as follows: filling the sorted nickel-copper powder into a rubber sleeve and sealing, filling the rubber sleeve into a plastic sleeve with the sealing position facing inwards, placing the plastic sleeve into an electrode mould, and performing compression molding at the pressure of 400-;
example 4:
the same as example 1 except that: in S1, vacuum induction melting and vacuumizing to 3 x 10-1Pa, heating to 1200K for vacuum induction melting.
Example 5:
the same as example 2 except that: the mass ratio of the mixed slagging agent to the melt raw material is 1: 5.
Example 6:
the same as example 2 except that: the mixed slag former is a cone-shaped material which is formed by pressing a slag former and a cosolvent according to the mass ratio of 10:9, and the slag former is CaO and SiO2The mass ratio of the auxiliary solvent to the auxiliary solvent is 1:1, and the auxiliary solvent is CaCl2。
Example 7:
the same as example 2 except that: the mixed slag former is a conical material which is formed by pressing a slag former and a protective agent in a mass ratio of 5:1, and the slag former is CaO and SiO2The protective agent consists of borax and magnesium in a mass ratio of 2:1 and 3: 1.
Example 8:
the same as example 2 except that: the mixed slag former is a cone-shaped material formed by pressing slag former, and the slag former is CaO and SiO2The weight ratio of the components is 2: 1.
Example 9:
essentially the same as example 3, except that: the high-temperature jet gas was 500K of argon gas, and the jet velocity of the high-temperature jet gas was 300 m/s.
Experimental example 1: research on the influence of different pretreatment processes on the purity of the nickel-copper alloy
The purification operation was performed on the raw material of nickel cupronickel produced in the same batch by the methods provided in example 1 and example 2, and the purification effects are shown in table 1:
table 1 table for detecting impurity content of nickel cupronickel prepared in examples 1 and 2
| Example 1 | Example 2 | Example 3 | |
| Percent of nickel and cupronickel impurity before purification | 6.83 | 6.82 | 6.83 |
| Percent impurity of nickel cupronickel after purification | 4.26 | 1.58 | 1.49 |
And (4) conclusion: the commercial nickel cupronickel raw material reacts with air in the processes of storage and transportation, an oxide layer is formed on the surface of the nickel cupronickel raw material, the oxide layer can influence the purification process, the oxide layer on the surface of the nickel cupronickel raw material can be removed by carrying out ultrasonic pickling and surface electrolysis on the nickel cupronickel raw material before the purification operation, but the purification efficiency can be obviously improved by carrying out slagging impurity removal or powder making impurity removal.
Experimental example 2: research on influence of vacuum degree and smelting temperature on purity of nickel-copper-nickel alloy in vacuum induction smelting process
The method provided by the embodiment 1 and the embodiment 4 are respectively used for purifying the nickel cupronickel raw material produced in the same batch, the comparison groups 1 and 2 are arranged, and the vacuum induction melting and the vacuumizing of the comparison group 1 are carried out to 2 multiplied by 10-1Pa, heating to 1100K for vacuum induction melting, and vacuumizing to 6 × 10 for vacuum induction melting of the control group 2-1Pa, heating to 1400K for vacuum induction melting, and the purification results are shown in Table 2:
TABLE 2 table for detecting the impurity content of nickel cupronickel prepared in examples 1 and 3 and control groups 1 and 2
| Example 1 | Example 4 | Control group 1 | Control group 2 | |
| Percent of nickel and cupronickel impurity before purification | 6.83 | 6.83 | 6.81 | 6.83 |
| Percent impurity of nickel cupronickel after purification | 3.89 | 5.21 | 5.38 | 5.46 |
And (4) conclusion: the vacuum degree and temperature of vacuum induction melting can affect the vacuum melting efficiency, and further affect the purification efficiency of the nickel cupronickel, and the impurity content of the nickel cupronickel raw material prepared under the vacuum degree and temperature in the embodiment 1 is the lowest.
Experimental example 3: study on the influence of the mass ratio of the mixed slag former to the melt raw material on the purity of the nickel white copper by using the methods provided in examples 2 and 5 to purify the nickel white copper raw material produced in the same batch, and setting reference groups 3 and 4, wherein the mass ratio of the slag former to the melt raw material in the reference group 3 is 1:4, the mass ratio of the slag former to the melt raw material in the reference group 4 is 1:9, and the purification results are shown in table 3:
TABLE 3 table for detecting impurity content of nickel cupronickel prepared in examples 1 and 4 and control groups 3 and 4
| Example 2 | Example 5 | Control group 3 | Control group 4 | |
| Percent of nickel and cupronickel impurity before purification | 6.82 | 6.81 | 6.81 | 6.83 |
| Percent impurity of nickel cupronickel after purification | 3.16 | 4.17 | 5.19 | 5.83 |
And (4) conclusion: the mass ratio of the mixed slag former to the melt raw material affects the purification efficiency of the nickel cupronickel, the mass ratio provided in example 2 is the optimal mass ratio, and the impurity content of the prepared nickel cupronickel is the lowest.
Experimental example 4: research on influence of different components of the mixed slag former on the purity of the nickel-copper alloy
The purification operations of the raw materials of nickel cupronickel produced in the same batch were performed by the methods provided in examples 2, 6, 7 and 8, respectively, and the purification effects are shown in table 4:
TABLE 4 table for detecting the impurity content of nickel cupronickel prepared in examples 2, 6, 7 and 8
| Example 2 | Example 6 | Example 7 | Example 8 | |
| Percent of nickel and cupronickel impurity before purification | 6.80 | 6.83 | 6.83 | 6.82 |
| Percent impurity of nickel cupronickel after purification | 2.89 | 5.27 | 5.30 | 5.69 |
And (4) conclusion: the slag former, the cosolvent and the protective agent in the mixed slag former all influence the purification efficiency of the nickel cupronickel, wherein the cosolvent can reduce the viscosity of the mixed slag former, increase the reaction rate and improve the removal rate of metal impurities, the protective agent can form a protective layer on the surface of a melt raw material to prevent the melt raw material from undergoing an oxidation reaction with oxygen in the air in the subsequent treatment, and the impurity content of the nickel cupronickel raw material prepared under the composition and the proportion of the slag former in the embodiment 2 is the lowest.
Experimental example 5: the influence of the temperature and the injection speed of the high-temperature injection gas on the particle size of the prepared solid powder and the influence of the particle size of the solid powder on the purity of the nickel-copper-nickel-copper alloy are researched
The method provided in example 3 and example 9 were used to purify the raw material of nickel cupronickel produced in the same batch, and the comparison groups 5 and 6 were set, wherein the high-temperature injection gas in the comparison group 5 was argon gas of 400K, the injection speed of the high-temperature injection gas was 200m/s, the high-temperature injection gas in the comparison group 6 was argon gas of 700K, and the injection speed of the high-temperature injection gas was 500m/s, and the parameter results of the prepared nickel cupronickel are shown in table 5:
TABLE 5 parameter tables for nickel cupronickel prepared in examples 3 and 9 and controls 5 and 6
| Example 3 | Example 9 | Control group 5 | Control group 6 | |
| Particle size/. mu.m of solid powder | 58 | 75 | 92 | 56 |
| Percent of nickel and cupronickel impurity before purification | 6.83 | 6.83 | 6.83 | 6.82 |
| Percent impurity of nickel cupronickel after purification | 2.16 | 4.17 | 5.20 | 2.15 |
And (4) conclusion: the nickel cupronickel impurity ratio produced by the high temperature spraying gas temperature and the spraying speed provided in example 3 was the lowest, and the solid powder particle size produced by the high temperature spraying gas temperature and the spraying speed provided in control group 6 was the lowest, but the high temperature spraying gas temperature and the spraying speed provided in example 3 were the most suitable because the apparatus capable of providing the spraying speed of 500m/s was too expensive, so that the production cost was greatly increased, and the difference between the high temperature spraying gas temperature and the spraying speed and the solid powder particle size produced in example 3 was not great.
Claims (9)
1. A method for improving the purity of a nickel cupronickel material is characterized by mainly comprising the following steps:
s1: pretreatment of
Acid washing: completely immersing the nickel-copper-nickel raw material in absolute ethyl alcohol, carrying out acid washing for 10-20min by using an ultrasonic cleaning device, and cleaning and drying the nickel-copper-nickel raw material;
surface treatment: placing the acid-washed nickel cupronickel raw material in electrolyte, and introducing current with density of 3-5A/cm2The current is used for carrying out surface layer electrolysis on the nickel cupronickel to remove an oxide layer on the surface of the nickel cupronickel, and a high-power blower is used for cleaning the surface of the nickel cupronickel;
s2: vacuum induction melting
Placing the pretreated nickel-copper white raw material in a vacuum induction melting furnace, preheating at 800--1Pa, heating to 1200-1300K, carrying out vacuum induction melting on the nickel cupronickel raw material to a molten state, and preparing a solid electrode through a mold material;
s3: vacuum consumable remelting
And (4) taking the solid electrode obtained in the step (S2) as a remelting electrode for vacuum consumable remelting, taking a water-cooled copper crucible as a consumable electrode to conduct arc striking between the two electrodes, and electrically melting the solid electrode into the water-cooled copper crucible for cooling to obtain the purified nickel cupronickel.
2. The method as claimed in claim 1, wherein the electrolyte in S1 comprises 2-3% hydrochloric acid, 1-2% oxalic acid, 3-5% citric acid, 1-2% ammonium sulfate, and the balance deionized water.
3. The method for improving the purity of the nickel cupronickel material as claimed in claim 1, wherein the raw material of the nickel cupronickel in S1 is subjected to slagging and impurity removal processes before acid washing according to the raw material purity: heating a nickel cupronickel raw material to 1000-1200K to obtain a melt raw material, adding a mixed slag former into the melt raw material, reacting the mixed slag former with impurities in the melt raw material to generate oxide residues, removing the oxide residues floating on the surface of the melt raw material by using slag removing equipment until no obvious oxide residues exist on the surface of the melt, and cooling the remaining melt raw material to obtain the nickel cupronickel raw material after impurity removal.
4. The method for improving the purity of the nickel cupronickel material as claimed in claim 3, wherein the mass ratio of the mixed slag former to the raw melt material is 1: 5-8.
5. The method for improving the purity of the nickel cupronickel material as claimed in claim 1, wherein the raw material of the nickel cupronickel in S1 is subjected to a powdering and impurity removing process before being subjected to acid washing according to the raw material purity: cutting a nickel-copper-nickel raw material into rod-shaped materials, clamping the rod-shaped materials on a smelting machine, carrying out electrode induction smelting until the rod-shaped materials are melted into liquid, allowing the liquid to fall through a settling tube under the action of gravity, blowing the liquid raw material into fine liquid drops by using high-temperature jet gas, condensing the liquid drops into solid powder in the settling process, sorting the solid powder to obtain nickel-copper-nickel powder, and carrying out cold isostatic pressing on the nickel-copper-nickel powder to obtain the nickel-copper-nickel raw material after impurity removal.
6. The method as claimed in claim 5, wherein the high temperature injection gas is argon at 500-.
7. The method as claimed in claim 5, wherein the spraying speed of the high temperature spraying gas is 300-400 m/s.
8. The method for improving the purity of the nickel cupronickel material as claimed in claim 5, wherein the specific process of the cold isostatic pressing is as follows: and (3) filling the sorted nickel cupronickel powder into a rubber sleeve and sealing, inward filling the rubber sleeve at the sealing position into a plastic sleeve, placing the plastic sleeve into an electrode mould, and performing compression molding at the pressure of 400-.
9. Use of a nickel cupronickel material prepared by the method of claim 1 in the manufacture of a medical x-ray tube.
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|---|---|---|---|---|
| CN114349486A (en) * | 2022-01-27 | 2022-04-15 | 登封市汇联磨料磨具有限公司 | Production method of brown corundum abrasive and sand-cutting equipment thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5348034A (en) * | 1976-10-15 | 1978-05-01 | Mitsubishi Metal Corp | Process for welding low alloy copper material and steel material |
| CN102690971A (en) * | 2012-01-10 | 2012-09-26 | 河南科技大学 | High-strength copper alloy strip and preparation method thereof |
| JP2015052166A (en) * | 2007-11-19 | 2015-03-19 | ハンチントン、アロイス、コーポレーションＨｕｎｔｉｎｇｔｏｎ Ａｌｌｏｙｓ Ｃｏｒｐｏｒａｔｉｏｎ | Ultra high strength alloy for severe oil and gas environment and method of preparation |
| CN109055801A (en) * | 2018-07-31 | 2018-12-21 | 陕西斯瑞新材料股份有限公司 | A kind of preparation method using vacuum consumable arc-melting CuFe alloy material |
-
2019
- 2019-12-18 CN CN201911309943.1A patent/CN111020257B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5348034A (en) * | 1976-10-15 | 1978-05-01 | Mitsubishi Metal Corp | Process for welding low alloy copper material and steel material |
| JP2015052166A (en) * | 2007-11-19 | 2015-03-19 | ハンチントン、アロイス、コーポレーションＨｕｎｔｉｎｇｔｏｎ Ａｌｌｏｙｓ Ｃｏｒｐｏｒａｔｉｏｎ | Ultra high strength alloy for severe oil and gas environment and method of preparation |
| CN102690971A (en) * | 2012-01-10 | 2012-09-26 | 河南科技大学 | High-strength copper alloy strip and preparation method thereof |
| CN109055801A (en) * | 2018-07-31 | 2018-12-21 | 陕西斯瑞新材料股份有限公司 | A kind of preparation method using vacuum consumable arc-melting CuFe alloy material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349486A (en) * | 2022-01-27 | 2022-04-15 | 登封市汇联磨料磨具有限公司 | Production method of brown corundum abrasive and sand-cutting equipment thereof |
| CN114349486B (en) * | 2022-01-27 | 2022-10-11 | 登封市汇联磨料磨具有限公司 | Production method of brown corundum abrasive and sand-cutting equipment thereof |
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